The reaction of 2,5-diphenylphosphacymantrene with solid KOH in the presence of crown ethers: Synthesis of the anionic η4-phosphoryl manganese complexes

Article abstract of DOI:10.1016/j.jorganchem.2009.09.013

2,5-Diphenylphosphacymantrene (1) reacts with solid KOH in the presence of crown ethers in C₆H₆ or CH₂Cl₂ at room temperature adding OH nucleophile to the phosphorus atom to afford anionic complexes [(CO)_3<

Full text of DOI:10.1016/j.jorganchem.2009.09.013

Journal of Organometallic Chemistry 694 (2009) 4121–4123
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Communication
The reaction of 2,5-diphenylphosphacymantrene with solid KOH in the presence
of crown ethers: Synthesis of the anionic
g
4-phosphoryl manganese complexes
*
Vasily V. Bashilov, Allan G. Ginzburg , Alexander F. Smol’yakov, Fedor M. Dolguschin,
Pavel V. Petrovskii, Viatcheslav I. Sokolov
A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28, Vavilov St., 119991 Moscow, Russian Federation
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 16 June 2009
Received in revised form 2 September 2009
Accepted 3 September 2009
Available online 11 September 2009
2,5-Diphenylphosphacymantrene (1) reacts with solid KOH in the presence of crown ethers in C6H6 or
CH2Cl2 at room temperature adding OH nucleophile to the phosphorus atom to afford anionic complexes
[(CO)3Mn-
g
4-2,5-Ph2H2C4P(@O)H]À [KÀCrown]+, where Crown = 18-crown-6 (2) or dicyclohexyl-18-
crown-6 (3). Complexes 2 and 3 are characterized by 1H, 31P, 13C NMR and IR-spectra. The structure of 2
is established by X-ray crystal structure data.
Ó 2009 Elsevier B.V. All rights reserved.
Keywords:
Manganese complexes
Phosphacymantrenes
Crown ethers
Nucleophilic addition
OH nucleophile
Phosphoryl rearrangement
1. Introduction
2. Results and discussion
(
g
5-Cyclopentadienyl)manganesetricarbonyl(cymantrene)
one of the most studied -complexes of transition metals with car-
is
We found that in dichloromethane at room temperature 1 can
p
react with solid KOH in the presence of 1 equiv. of a crown ether
bonyl ligands (for the recent review see Ref. [1]). Replacement of
to form anionic salt-like complexes [(CO)3Mn-g
4-2,5-
one CH group in the ligand for a heteroatom changes the property
of a compound greatly. Among this group of p-complexes phosph-
Ph2H2C4P(@O)H]À [KÀCrown]+, where Crown = 18-crown-6 (2) or
dicyclohexyl-18-crown-6 (3) (Scheme 1). In the absence of crown
ether the reaction 1 with KOH proceeds as well according to 31P
NMR-spectra, however, single crystals were not obtained. The reac-
tion has been monitored by 31P NMR-spectra but we have not been
able to detect any intermediate and registered only the transitions
1 ? 2 or 3. Probably the primary anionic intermediate is very unsta-
ble and quickly rearranges into the final anions 2À or 3À with the
migration of H from oxygen to phosphorus, counter ion being K+
complexed to crown ether. Similar rearrangements of the unstable
compounds of the type R2P(OH) (R = alkyl, aryl) into the stable
four-coordinated compounds R2P(@O)H are well-known in organo-
phosphorus chemistry [6,7].
Complexes 2 and 3 are solids stable in inert atmosphere and
characterized by IR, 1H, 13C and 31P NMR-spectra. Formation of
them is accompanied by the sharp changes in 31P NMR-spectra: in-
stead of a singlet, at À30.6 ppm (1), a doublet centered between 0
and 1 ppm arises with a great 1J(H–P) = 516 or 521 Hz for 2 or 3
which evidences the direct P–H bond.
acymantrenes have been investigated mostly by group of Mathey
[2–4]. According to quantum chemical calculations, the LUMO-
orbital in phosphacymantrenes is largely localized on the P atom
and by this reason the nucleophilic attack could be expected to
proceed on phosphorus atom [2,3]. Previously, it was established
that
g
5-3,4-dimethylphosphacymantrene (THF, À78 °C) when
reacting with PhLi or t-BuLi could add Ph or t-Bu groups on phos-
phorus. From the 31P NMR data it was proposed that unstable
intermediates with
g
4-type coordination of phospholyl ligand with
Mn were formed [3,4]. Later we found that 2,5-diphenylphospha-
cymantrene (1) reacts with Na2PdCl4 and NaOAc in ROH (R = Me,
Et) to form P-alkoxyderivatives [5]. We were interested to investi-
gate the addition of other nucleophilic reagents to that substrate.
In this communication we report on the reaction of 1 with solid
KOH in the presence of crown ethers.
The crystal structure of 2 is established by X-ray data. It is the
* Corresponding author. Fax: +7 499 135 5058.
E-mail address: allan@ineos.ac.ru (A.G. Ginzburg).
salt composed of the [(CO)3Mn-g
4-2,5-Ph2H2C4P]À anion and
0022-328X/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2009.09.013

4122
V.V. Bashilov et al. / Journal of Organometallic Chemistry 694 (2009) 4121–4123
cation K+ coordinated by six oxygen atoms of the crown ether
(Fig. 1).
The bond length P(1)@O(1P) 1.492(2) Å in 2 is almost equal to
the bond length P@O in the triphenylphosphinoxide (1.482 Å). In
crystal, both cation and anion are situated in general position. In
anion 2À five-membered cycle C4P is in the ‘‘envelope” conforma-
tion, P atom is going out from the plane C(1)–C(2)–C(3)–C(4) by
0.675 Å to the site opposite to the manganese atom. Distance
Mn(1)ÀP(1) 2.8081(7) Å exceeds considerably the sum of covalent
radii Mn (1.35 Å) and P (1.13 Å) [8]. The distance Mn(1)ÀP(1) in 2
is greatly elongated as compared to the bond lengths (Mn)–(P)
(2.368–2.422 Å) in the complexes with
as the ketone
5-2-benzoyl-3,4-dimethylphosphacymantrene [9]
(2.387(2) Å); complex (1) ? W(CO)5 [10] (2.376(3) Å); complex
(CO)2(L)Mn- where L = PPh3 [11]
5-3,4-Me2-2-CHO-C4HP,
g
5-phosphoryl ligand such
g
g
(2.420(1) Å). In these complexes P atom is going out from the plane
C(1)–C(4) no more than 0.048–0.050 Å, but in anion 2À this dis-
tance is 0.675 Å. From these data it may be concluded that bond
Mn–P in 2 is absent or very weak, and phosphoryl ligand is g4
-
coordinated with Mn. Besides that, a small change in the C–C bond
length in the five-membered ring is observed alternating as ‘‘long-
short-long” that evidences the violation of the
fragment. To our knowledge, complex 2 is the first anionic complex
with
4-coordinated to manganese phosphoryl ligand character-
ized by X-ray data. Earlier the highly relevant zwitterionic complex
(CO)3MnÀ- -3,4-Me2H2P+(Ph)(CH2CH2CO2Et) was described by
g
5-srtucture of that
g
g
Mathey and coworkers [3]. The noteworthy feature of this complex
was ‘‘a relatively weak P–Mn interaction at 2.7651(8) Å”. Crystal
structure of the related zwitterion complex (CO)3MnÀ-g4
-
(CRCRCRCRP+Me2) where R = CO2Me had been described by Lind-
ner et al. [12], but this complex did not contain P–Mn bond.
It is important to emphasize that cation K+ in crystal takes part
in two more coordinative interactions, with O atom of a phos-
phoryl group [K(1)–O(1P) 2.618(2) Å] and with oxygen atom of a
carbonyl group in a neighbor molecule [K(1)–O(1)x,0.5Ày,À0.5+z
Scheme 1.
Fig. 1. Molecular structure and numbering scheme for compound 2. Selected bond lengths (Å) and angles (°): Mn(1)–C(1) 2.172(3), Mn(1)–C(2) 2.084(3), Mn(1)–C(3)
2.078(3), Mn(1)–C(4) 2.155(3), Mn(1)–P(1) 2.8081(7), P(1)–O(1P) 1.492(2), P(1)–H(1P) 1.30(3), P(1)–C(1) 1.778(3), P(1)–C(4) 1.777(3), C(1)–C(2) 1.441(4), C(2)–C(3) 1.418(4),
C(3)–C(4) 1.438(3), K(1)–O(1P) 2.618(2), K(1)–O(1)x,0.5Ày,À0.5+z 2.772(2), K(1)–O(crown) 2.766(2)–2.859(2), C(1)–P(1)–C(4) 89.4(1), O(1P)–P(1)–H(1P) 110(1).

V.V. Bashilov et al. / Journal of Organometallic Chemistry 694 (2009) 4121–4123
4123
Fig. 2. Infinite chain in the crystal 2 formed due to the cation–anion K–O coordination bonds.
2.772(2) Å] to form the supramolecular structure as an infinite
chain along the crystallographic axes c (Fig. 2). This probably
points out to the strong delocalization of a negative charge in anion
over all oxygen atoms in phosphinoxide and carbonyl groups. A
0.20, dt, 1J(P–HP) 521.0, 3J(P–H3,4) = 13.6 Hz. IR-spectra (CH2Cl2):
(CO) 1890 and 1980 cmÀ1
m
.
3.2. X-ray crystal data for 2
relatively slight shift of
and 3 is also in accordance with a strong delocalization of negative
m
(CO) frequencies, 60 and 45 cmÀ1 in 2
The single crystals for X-ray study were obtained by slow diffu-
sion of pentane into the benzene solution of 2 in NMR-tube.
C31H37KO10PMn, M = 694.62, monoclinic, space group P21/c,
a = 20.372(1), b = 7.4744(5), c = 22.817(1) Å, b = 108.551(1)°,
charge (usually in anionic Mn complexes
or more).
Dm
(CO) is 80–100 cmÀ1
V = 3293.8(4) Å3, Dcalc = 1.401 g/cm3, Z = 4,
l
= 0.630 mmÀ1. Sin-
3. Experimental
gle-crystal X-ray diffraction experiment was carried out with a
Bruker SMART 1000 CCD diffractometer [14] (graphite monochro-
2,5-Diphenylphosphacymantrene (1) was prepared according to
the procedure [13]. 1H, 31P and 13C NMR-spectra were registered
using spectrometer Bruker–Avance 400 at 400.16 MHz for 1H,
161.9 MHz for 31P and 100.6 MHz for 13C. Chemical shifts were
mated Mo
Ka radiation, k = 0.71073 Å, x-scan technique,
T = 120 K). The H(1P) atom was localized from different Fourier
synthesis and involved in refining in isotropic approximation.
The refinement converged to wR2 = 0.1247 and GOF = 0.990 for all
7148 independent reflections [R1 = 0.0520 was calculated against
measured relative TMS (1H, 13C) or H3PO4 31P). Complexes 2 and
(
3 were obtained and handled under argon atmosphere.
F for 5710 observed reflections with I > 2r(I)], 401 refined param-
eters. The SHELXTL-97 program package [15] was used throughout
the calculations; CCDC reference number 735789.
3.1. Synthesis of complexes 2 (or 3)
Complex 2: 37.4 mg 1 (0.1 mmol) and 28 mg of 18-crown-6
(0.106 mmol) were dissolved in 3–4 ml CH2Cl2, one granule of solid
KOH (56–60 mg, ꢀ10-fold excess) was added and the mixture was
shaken from time to time at room temperature in the dark. After
ꢀ24 h on monitoring 31P NMR-spectra the starting compound 1 re-
acted to give 2 in quantitative yield. Excess of KOH was removed.
To yellow solution 10 ml of pentane were added, the light-yellow
crystals being formed. The crystals were washed twice with pen-
tane and dried in vacuum. Yield 44 mg. Anal. Calc. for
C31H37O10PKMn: C, 53.60; H, 5.37; P, 4.46. Found: C, 52.91; H,
5.33; P, 4.46%. Spectral data for 2. 1H NMR (CD2Cl2), d, ppm: 7.92
(dt, 1H, 1J(HP–P) = 516.0, 4J(HP–H3,4) = 2.3 Hz, P(O)H); 7.40 (d,
4H), 7.18 (t, 4H), 6.99 (t, 2H), 10H, o, m, p C6H5; 5.37 [dd, 2H,
3J(H3,4–P) = 13.7, 4J(H3,4–HP) = 2.3 Hz, H(3,4)]; 3.47 (s, 24H, CH2 in
crown ether). 31P NMR (CD2Cl2): d 0.95 ppm, dt, 1J(P–HP) = 516.0,
3J(P–H3,4) 13.7 Hz.
Supplementary material
CCDC 735789 contains the supplementary crystallographic data
for this paper. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
Acknowledgments
This work has been done under the financial support of the
Russian Foundation for Basic Research (Projects 08-03-00169 and
07-03-00631).
References
[1] A.G. Ginzburg, Usp. Khim. 78 (3) (2009) 211 (Russ. Chem. Rev. 78 (3) (2009)
211).
[2] C. Guimon, G. Pfister-Guilliouso, F. Mathey, Nouv. J. Chem. 3 (1979) 725.
[3] B. Deschamps, P. Toullec, L. Ricard, F. Mathey, J. Organomet. Chem. 634 (2001)
131.
[4] B. Deschamps, L. Ricard, F. Mathey, J. Organomet. Chem. 689 (2004) 4647.
[5] A.G. Ginzburg, V.V. Bashilov, F.M. Dolgushin, A.F. Smol’yakov, A.S. Peregudov,
V.I. Sokolov, J. Organomet. Chem. 694 (2009) 72.
[6] A. Michaelis, L. Gleichmann, Chem. Ber. 15 (1882) 801.
[7] A. Kirby, S.D. Warren, The organic chemistry of phosphorus, Elsevier,
Amsterdam, London, New York, 1967.
13C NMR (CD2Cl2), d, ppm: 228.8, Mn(CO)3; 140.9, key-C-atoms
of C6H5; 128.2, 125.3, 124.0, C-atoms of o,m,p-positions of C6H5;
79.3, d, J(13C–31P) = 17 Hz, two C-atoms in b-positions to P; 70.2,
C-atoms of crown ether; 66.7, d, J(13C–31P) = 91 Hz, two C-atoms
in
a
-positions to P.
IR-spectra (CH2Cl2):
m
(CO) 1890 cmÀ1 (broad, E-mode),
1980 cmÀ1 (A1-mode). IR-spectra in the solid state (nujol):
1872 (E-mode), 1964 cmÀ1 (A1-mode). For 1 (CH2Cl2):
1950 cmÀ1 (broad, E-mode), 2025 cmÀ1 (A1-mode).
m
m
(CO)
(CO)
[8] S.S. Batsanov, Zh. Neorg. Khim. 36 (1991) 3015 (Russ. J. Inorg. Chem. 36 (12)
(1991)).
[9] F. Mathey, A. Mitschler, R. Weiss, J. Am. Chem. Soc. 100 (1978) 5748.
[10] A.G. Ginzburg, A.S. Batsanov, Yu.T. Struchkov, J. Organomet. Chem. USSR 4
(1991) 417.
[11] B. Deschamps, L. Ricard, F. Mathey, Organometallics 18 (1999) 5688.
[12] E. Lindner, A. Rau, S. Hoehne, J. Organomet. Chem. 218 (1981) 41.
[13] A. Breque, F. Mathey, C. Santini, J. Organomet. Chem. 165 (1979) 129.
[14] SMART V5.051 and SAINT V6.01, Area Detector Control and Integration Software,
Bruker AXS, Madison, Wisconsin, USA, 1998.
Complex
3 prepared as described above from 25 mg 1
(0.067 mmol) and 25 mg of dicyclohexyl-18-crown-6 (0.067 mmol)
in 2.5–3 ml CH2Cl2, yield ꢀ30 mg.
Spectral data for 3: 1H NMR (CDCl3) d, ppm: 8.10 (dt, 1H, 1J(HP–
P) = 521.0, 4J(HP–H3,4) = 2.2 Hz, PH); 7.39 (d, 4H), 7.13 (t, 4H), 6.94
(t, 2H), 10H, o, m, p C6H5; 5.32 (dd, 3J(H3,4–P) = 13.6, 4J(H3,4
–
HP) = 2.2 Hz (2H, protons H(3,4)). The protons of crown ether
[15] G.M. Sheldrick, SHELXTL v. 5.10, Structure Determination Software Suite, Bruker
AXS, Madison, Wisconsin, USA, 1998.
appear as two multiplets at 3.41 and 1.24. 31P NMR-spectra: